Effects of low-energy electron bombardment on the surface chemical structure and adhesive properties of polytetrafluoroethylene (PTFE)

The x-ray photoemission studies of polytetrafluoroethylene (PTFE) bombarded by lowenergy electrons in ultra-high vacuum conditions indicate that the major chemical changes induced by electron bombardment are defluorination of the surface and cross-linking of the polymer chains. The same electron bombardment process, when performed in the presence of 1×10⁻⁶ Torr ND₃, also results in the adsorption of nitrogen-containing groups at the surface. The rate of nitrogen adsorption is linear for short electron bombardment times while the rates of defluorination and cross-linking are roughly exponential. However, at long bombardment times, the rates of nitrogen uptake, defluorination, and cross-linking become zero at the same time, indicating that defluorination of the surface is the rate-determining step in electron beam-induced adsorption of nitrogen-containing species. Regardless of whether the bombardment is carried out in ultra-high vacuum or in the presence of ND₃, the maximum modification depth is less than 30 Å. Pull tests performed on PTFE samples bombarded by electrons in ultra-high vacuum, then removed into air and bonded to epoxy show epoxy-PTFE joint strengths of 280–360 1b/in.² (psi), are compared to zero psi for untreated PTFE and ≃2000 psi for cohesive failure within the PTFE layer.